EP1892280A1 - Fluid catalytic cracking of oxygenated compounds - Google Patents

Fluid catalytic cracking of oxygenated compounds Download PDF

Info

Publication number
EP1892280A1
EP1892280A1 EP06118982A EP06118982A EP1892280A1 EP 1892280 A1 EP1892280 A1 EP 1892280A1 EP 06118982 A EP06118982 A EP 06118982A EP 06118982 A EP06118982 A EP 06118982A EP 1892280 A1 EP1892280 A1 EP 1892280A1
Authority
EP
European Patent Office
Prior art keywords
glycerol
catalyst
catalytic cracking
oxygenated hydrocarbon
injection point
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP06118982A
Other languages
German (de)
English (en)
French (fr)
Inventor
Paul O'connor
George W. Huber
Avelino Corma Camos
Laurent Sauvanaud
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bioecon International Holding NV
Original Assignee
Bioecon International Holding NV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bioecon International Holding NV filed Critical Bioecon International Holding NV
Priority to EP06118982A priority Critical patent/EP1892280A1/en
Priority to US12/377,388 priority patent/US8207385B2/en
Priority to CA2660755A priority patent/CA2660755C/en
Priority to PCT/EP2007/058467 priority patent/WO2008020047A2/en
Priority to BRPI0715873-4A2A priority patent/BRPI0715873A2/pt
Priority to EP07802626A priority patent/EP2059576A2/en
Priority to CNA200780038305XA priority patent/CN101558135A/zh
Priority to JP2009524192A priority patent/JP2010500464A/ja
Priority to KR1020097005405A priority patent/KR20090052363A/ko
Priority to MX2009001721A priority patent/MX2009001721A/es
Publication of EP1892280A1 publication Critical patent/EP1892280A1/en
Priority to CO09027098A priority patent/CO6190561A2/es
Priority to US13/196,489 priority patent/US8524960B2/en
Withdrawn legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/54—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids characterised by the catalytic bed
    • C10G3/55—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids characterised by the catalytic bed with moving solid particles, e.g. moving beds
    • C10G3/57—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids characterised by the catalytic bed with moving solid particles, e.g. moving beds according to the fluidised bed technique
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/14—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts
    • C10G11/18—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts according to the "fluidised-bed" technique
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/42—Catalytic treatment
    • C10G3/44—Catalytic treatment characterised by the catalyst used
    • C10G3/45—Catalytic treatment characterised by the catalyst used containing iron group metals or compounds thereof
    • C10G3/46—Catalytic treatment characterised by the catalyst used containing iron group metals or compounds thereof in combination with chromium, molybdenum, tungsten metals or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/42—Catalytic treatment
    • C10G3/44—Catalytic treatment characterised by the catalyst used
    • C10G3/47—Catalytic treatment characterised by the catalyst used containing platinum group metals or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/42—Catalytic treatment
    • C10G3/44—Catalytic treatment characterised by the catalyst used
    • C10G3/48—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support
    • C10G3/49—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support containing crystalline aluminosilicates, e.g. molecular sieves
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G51/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more cracking processes only
    • C10G51/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more cracking processes only plural serial stages only
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G51/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more cracking processes only
    • C10G51/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more cracking processes only plural serial stages only
    • C10G51/026—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more cracking processes only plural serial stages only only catalytic cracking steps
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1011—Biomass
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1074—Vacuum distillates
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4006—Temperature
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/80—Additives
    • C10G2300/805—Water
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

Definitions

  • This invention relates to a process for production of olefins, aromatic, syn-gas (hydrogen, carbon monoxide), process heat, and coke by co-feeding oxygenated compounds, such as glycerol, carbohydrates, sugar alcohols or other oxygenated biomass-derived molecules such as starches, cellulose, and hemicellulose-derived compounds) with petroleum derived feedstocks in a modified fluid catalytic cracking process.
  • oxygenated compounds such as glycerol, carbohydrates, sugar alcohols or other oxygenated biomass-derived molecules such as starches, cellulose, and hemicellulose-derived compounds
  • Fluid catalytic cracking is the most widely used process for the conversion of crude oil into gasoline, olefins and other hydrocarbons.
  • the FCC process consists of two vessels coupled together as shown in Fig. 1. ln the first reactor a hot particulate catalyst is contacted with hydrocarbon feedstocks, thereby producing cracked products and spent coked catalyst. After the cracking reaction takes place the catalyst is largely deactivated by coke.
  • the coked catalyst is separated from the cracked products, stripped of residual oil by steam stripping and then regenerated by burning the coke from the deactivated catalyst in a regenerator.
  • the hot catalyst is then recycled to the riser reactor for additional cracking.
  • a variety of process configurations and catalysts have been developed for the FCC process.
  • the heart of the FCC catalyst is a faujasite zeolite. New medium, large and extra-large pore zeolites are actively searched to achieve a higher flexibility in product distribution.
  • H/C eff effective hydrogen to carbon ratio
  • the H/C e ff ratio of biomass derived-oxygenated hydrocarbon compounds is lower than petroleum-derived feedstocks due to the high oxygen content of biomass-derived molecules.
  • the H/C eff ratio of carbohydrates, sorbitol and glycerol (all biomass-derived compounds) are 0, 1/3 and 2/3 respectively.
  • the H/ Ceff ratio of petroleum-derived feeds ranges from 2 (for liquid alkanes) to 1 (for benzene).
  • biomass can be viewed as a hydrogen deficient molecule when compared to petroleum-based feedstocks.
  • H / C eff H - 2 ⁇ O - 3 ⁇ N - 2 ⁇ S C
  • H, C, O, N and S are the moles of hydrogen, carbon, oxygen, nitrogen and sulfur respectively.
  • Glycerol is currently a valuable by-product of biodiesel production, which involves the transesterification of triglycerides to the corresponding methyl or ethyl esters.
  • biodiesel production increases, the price of glycerol is projected to drop significantly. In fact, the price of glycerol has already dropped by almost half over the last few years. [McCoy, 2005 #6] Therefore it is desirable to develop inexpensive processes for the conversion of glycerol into chemicals and fuels.
  • Solid materials including lignin, humic acid, and coke are byproducts of the above reaction.
  • a wide range of products are produced from the above reactions including: cellulose, hemicellulose, lignin, polysaccharides, monosaccharides (e.g. glucose, xylose, galatose), furfural, polysaccharides, and lignin derived alcohols (coumaryl, coniferyl and sinapyl alcohols).
  • Bio-oils produced by fast pyrolysis or liquefaction of biomass, are a mixture of more than 300 compounds. Bio-oils are thermally unstable, and need to be upgraded if they are to be used as fuels. Bio-oils, and bio-oil components, can be converted to more stable fuels using zeolite catalysts. [Bridgwater, 1994 #14] Reaction conditions used for the above process are temperatures from 350-500 °C, atmospheric pressure, and gas hourly space velocities of around 2. The products from this reaction include hydrocarbons (aromatic, aliphatic), water-soluble organics, water, oil-soluble organics, gases (CO 2 CO, light alkanes), and coke.
  • hydrocarbons aromatic, aliphatic
  • Bakhshi and co-workers studied zeolite upgrading of wood derived fast-pyrolysis bio-oils and observed that between 30-40 wt% of the bio-oil formed coke or char. (Sharma and Bakhshi 1993; Katikaneni, Adjaye et al. 1995; Adjaye, Katikaneni et al. 1996)
  • the ZSM-5 catalyst produced the highest amount (34 wt% of feed) of liquid organic products of any catalyst tested.
  • the products in the organic carbon were mostly aromatics for ZSM-5, and aliphatics for SiO 2 -Al 2 O 3 .
  • Gaseous products include CO 2 , CO, light alkanes, and light olefins.
  • Bio-oils are thermally unstable and thermal cracking reactions occur during zeolite upgrading. Bakhshi and co-workers also developed a two-reactor process, where only thermal reactions occur in the first empty reactor, and catalytic reactions occur in the second reactor that contains the catalyst. (Srinivas, Dalai et al. 2000) The reported advantage of the two-reactor system is that it improved catalyst life by reducing the amount of coke deposited on the catalyst.
  • model bio-oil compounds including alcohols, phenols, aldehydes, ketones, acids, and mixtures.
  • Alcohols were converted into olefins at temperatures around 200 °C, then to higher olefins at 250 °C, followed by paraffins and a small proportion of aromatics at 350 °C.
  • Phenol has a low reactivity on HZSM-5 and only produces small amounts of propylene and butanes.
  • 2-Methoxyphenol also has a low reactivity to hydrocarbons and thermally decomposes, generating coke.
  • Acetaldehyde had a low reactivity on ZSM-5 catalysts, and it also underwent thermal decomposition leading to coking problems.
  • Acetone which is less reactive than alcohols, converts into C 5+ olefins at temperatures above 350°C. These olefins are then converted into C 5+ paraffins, aromatics and light alkenes.
  • Acetic acid is first converted to acetone, and that then reacts as above.
  • Products from zeolite upgrading of acetic acid and acetone give considerably more coke than products from alcohol feedstocks.
  • different molecules in the bio-oils have a significant difference in reactivity and coke formation rates.
  • Catalytic cracking of vegetable oil can be used to produce a liquid fuel that contains linear and cyclic paraffins, olefins, aldehydes, ketones, and carboxylic acids.
  • the cracking of vegetable oils has been studied since 1921, and pyrolysis products of vegetable oils were used as a fuel during the 1 st and 2 nd World Wars. Both homogeneous and heterogeneous reactions are occurring during catalytic cracking of vegetable oils.
  • the pyrolysis reaction can be done with or without a catalyst, and a number of catalysts have been tested including HZSM-5, ⁇ -zeolite, and USY. 60,61 Twaiq et al.
  • This invention generally relates to a process for fluid catalytic cracking of oxygenated hydrocarbon compounds, comprising the step of contacting a reaction feed comprising an oxygenated hydrocarbon compound with a fluid cracking catalyst material for a period of less than 3 seconds, at a temperature in the range of 300 to 700 °C.
  • This invention more specifically relates to a process for production of olefins, aromatic, syn-gas (hydrogen, carbon monoxide), process heat, alkanes, and coke by co-feeding of glycerol, carbohydrates, sugar alcohols or other biomass derived molecules with high concentrations of oxygen (including starches, cellulose-derived compounds, and hemicellulose-derived compounds) with petroleum derived feedstocks in a modified fluid catalytic cracking process. Mixtures of these compounds, such as those found in bio-oils derived from pyrolysis or liquefaction, are also included in the biomass-derived oxygenate definition.
  • Fig. 1 is a flow diagram of a typical FCC process.
  • Fig. 2 is a flow diagram of a modified FCC process for co-feeding biomass-derived oxygenated hydrocarbon compounds with petroleum feedstocks.
  • Fig. 3 shows hydrogen producing reactions for catalytic cracking of biomass.
  • Fig. 4 shows hydrogen consuming reactions for catalytic cracking of biomass.
  • Fig. 5 shows the effect of catalyst composition on the catalytic cracking of a 50 wt% glycerol-water solution in MAT reactor.
  • Key Filled Diamonds-FCC1, Filled Squares- ZSM5, Triangies-ECat, Circles-Al 2 O 3 , Open Squares-silicon-carbide, Open Diamonds-Y-zeolite.
  • Fig. 6 shows the effect of catalyst composition on gas phase yields for the catalytic cracking of a 50 wt% glycerol-water solution in MAT reactor.
  • Key Filled Diamonds-FCC1, Filled Squares- ZSM5, Triangles-ECat, Circles-Al 2 O 3 , Open Squares-silicon-carbide, Open Diamonds-Y-zeolite.
  • Fig. 7 shows the effect of catalyst composition on the olefin-to-paraffin ratio and C 4 isomer-to-paraffin ratio for the catalytic cracking of a 50 wt% glycerol-water solution in MAT reactor.
  • Key Filled Diamands-FCC1, Filled Squares- ZSM5, Triangies-ECat, Circles-Al 2 O 3 , Open Squares-silicon-carbide, Open Diamonds-Y-zeolite. Glycerol fed into reactor as a 50 wt% glycerol-water mixture. Yields are based on carbon molar selectivity. Conversion includes coke plus gases plus aromatics.
  • Fig. 8 shows the effect of temperature on the catalytic cracking of a 50 wt% glycerol-water solution with ZSM-5 catalyst in MAT reactor.
  • Key Squares - 500 °C, Triangles-600 °C, Circles-700 °C.
  • Fig. 9 shows the effect of temperature on gas-phase yields for the catalytic cracking of a 50 wt% glycerol-water solution with ZSM-5 catalyst in MAT reactor.
  • Key Squares - 500 °C, Triangles-600 °C, Circles-700 °C.
  • Fig. 10 shows the effect of temperature on olefin-to-paraffin ratio for the catalytic cracking of a 50 wt% glycerol-water solution with ZSM-5 catalyst in MAT reactor.
  • Key Squares - 500 °C, Triangles-600 °C, Circles-700 °C.
  • Fig. 11 shows the catalytic cracking of 50 wt% glycerol and 50 wt% sorbitol aqueous solutions using ZSM-5 and silicon-carbide catalysts in MAT reactor at 500 °C.
  • Key Filled Squares-Glycerol with ZSM-5, Filled Triangles-Sorbitol with ZSM-5, Open Squares-Glycerol with SiC, Open Triangles-Sorbitol with SiC. Conversion includes coke plus gases plus aromatics.
  • Fig. 12 shows the gas phase-yields of 50 wt% glycerol and 50 wt% sorbitol aqueous solutions for catalytic cracking using ZSM-5 catalyst in MAT reactor at 500 °C. (Key: Squares-Glycerol, Triangles-Sorbifiol. Conversion includes coke plus gases plus aromatics.)
  • Fig. 13 shows the Olefin-to-Paraffin Ratio for 50 wt% glycerol and 50 wt% sorbitol aqueous solutions for catalytic cracking using a ZSM-5 catalyst in MAT reactor at 500 °C. (Key: Squares-Glycerol, Triangles-Sorbitol. Conversion includes coke plus gases plus aromatics.)
  • Fig. 14 shows the catalytic cracking of mixtures of vacuum gas oil (VGO) with 50 wt% glycerol, using FCC1 catalyst in MAT reactor at 500 °C.
  • Key Open Squares: Glycerol, Filled Squares: Glycerol-VGO 1-2 Volume Mixtures, Filled Circle: Glycerol-VGO 1-9 Volume Mixtures, and Filled Triangle: VGO.
  • Dotted line represents yields if an additive effect of glycerol and VGO were observed.
  • Conversion for VGO and glycerol-VGO mixtures includes gases plus coke plus gasoline fraction from simulated distillation. Conversion for pure glycerol feed includes coke plus gases plus aromatics.
  • Fig. 15 shows the gas phase yields and micromoles H 2 produced in catalytic cracking of mixtures of vacuum gas oil (VGO) with 50 wt% glycerol using FCC1 catalyst in MAT reactor at 500 °C.
  • VGO vacuum gas oil
  • Filled Squares Glycerol-VGO 1-2 Volume Mixtures
  • Filled Circle Glycerol-VGO 1-9 Volume Mixtures
  • Filled Triangle VGO.
  • VGO and glycerol-VGO mixtures include gases plus coke plus gasoline fraction from simulated distillation.
  • Conversion for pure glycerol feed includes coke plus gases plus aromatics.
  • Fig. 16 shows olefin-to-paraffin ratios for catalytic cracking of mixtures of vacuum gas oil (VGO) with 50 wt% glycerol using FCC1 catalyst in MAT reactor at 500 °C.
  • Key Open Squares: Glycerol, Filled Squares: Glycerol-VGO 1-2 Volume Mixtures, Filled Circle: Glycerol-VGO 1-9 Volume Mixtures, and Filled Triangle: VGO.
  • Conversion for VGO and glycerol-VGO mixtures includes gases plus coke plus gasoline fraction from simulated distillation. Conversion for pure glycerol feed includes coke plus gases plus aromatics.
  • This invention generally relates to a process for fluid catalytic cracking of oxygenated hydrocarbon compounds, comprising the step of contacting a reaction feed comprising an oxygenated hydrocarbon compound with a fluid cracking catalyst material for a period of less than 3 seconds, at a temperature in the range of 300 to 700°C. In a preferred embodiment the contact time is less than 1 second.
  • the contact time is defined as 1/GHSV, wherein GHSV stands for Gas Hourly Space Velocity. It will be understood that the contact time referred herein is the mean contact time of the oxygenated hydrocarbon compounds with the fluid cracking catalyst material. Individual oxygenated hydrocarbon molecules may have contact times that are longer or shorter than the mean. The skilled person will further appreciate that the mean residence time of the catalyst particles in the reactor may be different from the mean contact time as defined herein, in the sense that the mean residence time of the catalyst particles in the reactor may be longer than the mean contact time, but not shorter.
  • This invention more specifically relates to a process for production of olefins, aromatics, syn-gas (hydrogen, carbon monoxide), process heat, alkanes, and coke by co-feeding of glycerol, carbohydrates, sugar alcohols or other biomass derived oxygenated compounds such as starches, cellulose-derived compounds, and hemicellulose-derived compounds with petroleum derived feedstocks in a standard or modified fluid catalytic cracking process.
  • Mixtures of oxygenated compounds such as those found in bio-oils derived from pyrolysis or liquefaction, are also included in the definition of biomass-derived oxygenated compound.
  • oxygenated hydrocarbon compounds that have been produced via the liquefaction of a solid biomass material are particularly preferred.
  • oxygenated hydrocarbon compounds are produced via a mild hydrothermal conversion process, such as described in co-pending application EP 061135646, filed on May 5, 2006 , the disclosures of which are incorporated herein by reference.
  • oxygenated hydrocarbon compounds are produced via a mild pyrolysis process, such as described in co-pending application EP 061135679, filed on May 5, 2006 , the disclosures of which are incorporated herein by reference.
  • the oxygenated hydrocarbon compounds may be mixed with an inorganic material, for example as a result of the process by which they were obtained.
  • solid biomass may have been treated with a particulate inorganic material in a process such as described in co-pending application EP 061135810, filed May 5, 2006 , the disclosures of which are incorporated herein by reference. These materials may subsequently be liquefied in the process of EP 061135646 or that of EP 061135679 , cited herein above.
  • the resulting liquid products contain the inorganic particles. It is not necessary to remove the inorganic particles from the oxygenated hydrocarbon compounds prior to the use of these compounds in the process of the present invention. To the contrary, it may be advantageous to leave the inorganic particles in the oxygenated hydrocarbon feed, in particular if the inorganic material is a catalytically active material.
  • reaction feed may comprise significant amounts of water. This is particularly advantageous, because feedstocks such as bio-oil and glycerol derived from biomass conversion processes tend to be mixed with water. For example, a biodiesel transesterification process produces glycerol and water in a 1:3 molar ratio.
  • the process of the present invention does not require water to be removed from the oxygenated material prior to their being fed into the catalytic cracking reactor.
  • reaction feed further comprises a crude oil-derived material, for example vacuum gas-oil.
  • the biomass-derived oxygenated compounds can be fed in different locations in the FCC process, as shown in Figure 2, including: (1) in a separate riser reactor, (2) before introduction of vacuum gas-oil, (3) with vacuum gas-oil, or (4) after vacuum gas-oil on a partially deactivated catalyst.
  • best results are obtained when the oxygenated compounds are fed into a separate riser reactor (option (1)), or in the main riser reactor after the vacuum gas-oil (option (4)), because it allows for short contact times of the oxygenated compounds with the fluid catalytic cracking catalyst material. It is also possible to feed the oxygenated compound into the stripper.
  • VGO vacuum gas-oil
  • the cracking catalyst material for use in the present invention may be a conventional FCC catalyst material.
  • FCC catalysts generally comprise a zeolite, such as zeolite USY, a matrix material, such as alumina, and a kaolin clay.
  • the catalyst may further comprise additives for trapping metal contaminants, for converting sulphur compounds, and the like, as will be readily understood by a person skilled in the FCC art.
  • the cracking catalyst material comprises a basic material.
  • suitable basic materials include layered materials, and materials obtained by heat-treating layered materials.
  • the layered materials are selected from the group consisting of smectites, anionic clays, layered hydroxy salts, and mixtures thereof.
  • Hydrotalcite-like materials, in particular Mg-Al and Ca-Al anionic clays, are particularly preferred. It has surprisingly been found that basic materials are suitable for the cracking of a crude-oil derived material, such as VGO, as may be used as a first feedstock in certain embodiments of the process of the present invention.
  • the basic catalytic materials may be used as such, or may be used in admixture with a conventional FCC cracking catalyst.
  • the conversion of biomass-derived oxygenated hydrocarbon compounds in the FCC process occurs mainly through a series of dehydration, hydrogen producing, hydrogen consuming, and aromatic forming reactions.
  • Figures 3 and 4 we use glycerol to represent biomass-derived oxygenated hydrocarbon compounds.
  • H 2 may be produced through steam-reforming or direct dehydrogenation of the carbohydrates and hydrocarbons, water-gas shift, and decarbonylation of partially dehydrated species as shown in Figure 3. These reactions may produce CO, CO 2 , and coke as well as hydrogen.
  • the hydrogen produced in these reactions may be consumed in reactions that increase the H/C eff ratio of the products as shown in Figure 4, leading to olefins and alkanes.
  • Hydrogen may be exchanged directly through hydrogen transfer reactions between two hydrocarbon/ carbohydrates chains, or through consecutive dehydrogenation /hydrogenation processes. Hydrogen transfer reactions occur on acid sites, while dehydrogenation/ hydrogenation reactions are greatly accelerated by the presence of a metal. Aromatics are produced during this process probably by a diels-alder reaction and condensation of olefins and partially dehydrated/hydrogenated species. To selectively produce olefins and aromatics, the dehydration, hydrogen producing and hydrogen transfer reactions must be properly balanced by choosing the proper catalysts and reaction conditions.
  • the process of the present invention provides (1) fuels that are obtained from sustainable biomass resources, (2) a reduction in CO 2 emissions from petroleum plants, (3) a reduction of the amount of petroleum feedstocks in a petroleum refinery and (4) utilization of FCC technology that is already developed and in use in petroleum refineries therefore co-feeding of biomass into an FCC unit would not require a significant capital investment.
  • MAT Microactivity test
  • the catalyst was regenerated at a temperature of 813 K for 3 hours, in a 100 ml/min stream of air.
  • the gases were analyzed using a Varian 3800-GC equipped with three detectors, a Thermal Conductivity Detector (TCD) for analysis of H 2 and N 2 , which were separated in a 15 m molecular sieve column, and a Flame Ionization Detector (FID), and for C 1 to C 6 hydrocarbons separated in a 30 m Plot l Al 2 O 3 column.
  • Simulated distillation of the liquids was carried out with a Varian 3800-GC following the ASTM-2887-D procedure. Cuts were made at 423.8 K for light gasoline, 489.3 K for heavy gasoline and 617.1 K for LCO.
  • the CO 2 formed during the regeneration step was monitored and quantified by means of an IR cell.
  • Carbon yields are defined below as the moles of carbon in the produced divided by the moles of carbon in the feed. All conversions below are reported on a per carbon basis.
  • Hydrogen selectivity defined below as the moles of hydrogen divided by the potential moles of hydrogen produced. The potential moles of hydrogen produced are the moles of produced carbon times the hydrogen to carbon ratio in the feed plus the moles of CO 2 produced.
  • the Y-zeolite was CBU 500, steamed for 4 h at 816°C.
  • the ZSM-5 zeolite was mixed with a clay binder, to around 15% weight.
  • a glycerol solution was prepared with 99.5 weight percent glycerol (Aldrich Chemicals) diluted at a 1:1 weight ratio (about a 1:5 molar ratio glycerol:water) with distilled water.
  • a sorbitol solution was prepared with 99% sorbitol and the same water 1:1 weight ratio water dilution.
  • Petroleum-derived feeds typically contain metal impurities (V, Ni and Fe), which deposit themselves onto the catalyst during the FCC reaction.
  • V, Ni and Fe metal impurities
  • FCC equilibrium catalyst(ECAT) containing 4400ppm V and 1600ppm Ni. This catalyst gave a lower activity than the fresh FCC1 catalyst, as could be expected from the higher content of zeolite and surface area of the latter.
  • the product selectivity for the FCC1 and ECAT catalyst was very similar, indicating that V and Ni have little or no catalytic effect.
  • Thermal cracking of glycerol was studied by using an "inert" SiC material. The low activity of the "inert” SiC shows that glycerol has a high thermal stability, and thermal reactions are negligible in comparison to the catalytic transformation.
  • FCC catalysts contain Al 2 O 3 SiO 2 -Al 2 O 3 and Y-zeolite in the catalyst matrix.
  • the Al 2 O 3 catalyst had similar gas and coke yields as the FCC1 and ECat catalysts.
  • the gas-phase yields for Al 2 O 3 where also similar to those of FCC1 and ECat, with the exception that Al 2 O 3 has higher H 2 and ethane yields, and lower propylene, n-butane, butane, and aromatic yields, than FCC1 and ECat.
  • the Y-zeolite had a catalytic activity similar to the FCC1 catalyst.
  • the coke yield was slightly higher for Y-zeolite than FCC1.
  • the aromatic yield was lower for the Y-zeolite than for FCC1.
  • the other differences between Y-zeolite and FCC1 are that the Y-zeolite gave a lower CO 2 yield and higher C 1 -C 4 alkane and H 2 yields than the FCC1 catalyst.
  • the olefin yields for the Y-zeolite and FCC1 catalyst were similar, therefore the olefin to paraffin ratios for the Y-zeoiite were lower than the FCC1 1 catalyst.
  • ZSM-5 is a well known catalyst additive for FCC catalysts, so we also tested the activity of the ZSM-5 catalyst for catalytic cracking of glycerol.
  • the major difference with ZSM-5 and the other catalysts tested is that ZSM-5 had a lower coke yield (less than 20 %) and gave a higher yield of gases and aromatics. This is probably due to the smaller pore size of ZSM-5 zeolite, which makes it difficult for larger aromatic coke precursors to form inside the small ZSM-5 pores.
  • the activity of the catalysts decreased as Y ⁇ FCC1 > Al 2 O 3 > ZSM5 > ECat >> SiC.
  • the aromatics yield increased linearly with conversion for the ZSM5 catalyst, but first increased and then decreased with further increasing conversion for the FCC1, Y, ECat and Al 2 O 3 catalysts. It has been extensively shown with hydrocarbon cracking that the small ZSM-5 zeolite pore channels make it difficult for aromatics to condensate. Higher yields of coke were seen on the Y, ECat and FCC1 catalysts, due to the larger cage diameter of the Y-zeolite catalyst as well as an extensive mesopore volume which allows higher aromatics condensation, leading to coke formation.
  • the gas phase-carbon yields for ZSM5 decreased in the order CO > ethylene > propylene > CO 2 > butene > methane > ethane > propane > n-butane.
  • the ZSM5 catalyst gave a much higher ethylene yield and lower methane yield than the other catalysts, which may indicate that, on ZSM5, ethylene may be formed through decarbonylation of an oxygenated intermediate rather than via the cracking of longer chain hydrocarbons.
  • the olefin-to-paraffin ratio for these catalysts was greater than 10 in most cases, as shown in Figure 7.
  • the olefin-to-paraffin ratio for C 2 compounds was extremely high (e.g. greater than 60) for the ZSM5 catalyst.
  • the C 3 and C 4 olefin to paraffin ratio decreased as the conversion increased, which goes in parallel with the increases in coke.
  • the olefin-to-paraffin ratio for iso-C 4 compounds decreased in the order Al 2 O 3 > FCC1 > ECat > ZSM5 > Y.
  • Figures 8-10 show the effect of temperature on the catalytic cracking of glycerol with ZSM5.
  • the activity for cracking of glycerol increased with temperature, as shown in Figure 8.
  • the coke yield significantly decreased ( Figure 8)
  • the CO, H 2 , and ethylene yields increased ( Figure 9).
  • Similar temperature effects were observed for catalytic cracking of glycerol with FCC1.
  • 500 °C the coke yield increased linearly with conversion, whereas at 600 and 700 °C the coke yield did not increase with conversion.
  • the gas phase yields for glycerol and sorbitol are shown in Figure 12. The main differences between the two feeds are that sorbitol had a higher CO yield than glycerol feeds with the ZSM-5 catalyst. The CO and CO 2 yield is also higher for the thermal sorbitol reaction with SiC as the "catalyst" ('1-2 % CO yield at conversions 4-18) than for glycerol (0.3-0.5 % CO yield at conversions 2-8 %).
  • the glycerol solution gave a higher yield to gas, aromatics and coke than VGO.
  • An increase in the amount of glycerol in the VGO-glycerol mixtures slightly increased the conversion. Selectivity effects were barely seen with the 9:1 VGO-glycerol mixture. Apparently the amount of biomass was too small to produce significant changes in the different yields.
  • the 2:1 VGO-glycerol mixture introduced an important dilution of the VGO feedstock (at least 3/1 molar ratio between VGO feed molecules and glycerol/water mixture), and significant effects on gas and coke yields were observed.
  • VGO VGO
  • glycerol produces more coke, ethylene and propylene than VGO.
  • Adding glycerol to VGO significantly increased the amount of coke, but in a proportion similar to what would be observed as an additive effect.
  • Addition of glycerol to VGO did not change the gasoline yield, but did decrease the light cycle oil (LCO) yield because of a dilution effect with the glycerol feed, as glycerol cracking does not produce LCO fragment but some gasoline-range fragments, including some oxygenated hydrocarbon compounds.
  • LCO light cycle oil
  • a surprising effect from this example is that the ethylene and propylene yields for the VGO:glycerol mixtures was higher than what would be expected from an additive effect, as shown in Figure 14.
  • glycerol cracking produced significant amounts of CO and CO 2 , a similar yield of hydrogen, more methane and ethylene but less ethane, more propylene but less propane, and much less butanes and butane.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
EP06118982A 2006-08-16 2006-08-16 Fluid catalytic cracking of oxygenated compounds Withdrawn EP1892280A1 (en)

Priority Applications (12)

Application Number Priority Date Filing Date Title
EP06118982A EP1892280A1 (en) 2006-08-16 2006-08-16 Fluid catalytic cracking of oxygenated compounds
EP07802626A EP2059576A2 (en) 2006-08-16 2007-08-15 Fluid catalytic cracking of oxygenated compounds
CA2660755A CA2660755C (en) 2006-08-16 2007-08-15 Fluid catalytic cracking of oxygenated compounds
PCT/EP2007/058467 WO2008020047A2 (en) 2006-08-16 2007-08-15 Fluid catalytic cracking of oxygenated compounds
BRPI0715873-4A2A BRPI0715873A2 (pt) 2006-08-16 2007-08-15 processo para o craqueamento catalÍtico de fluido de compostos de hidrocarbonetos oxigenados
US12/377,388 US8207385B2 (en) 2006-08-16 2007-08-15 Fluid catalytic cracking of oxygenated compounds
CNA200780038305XA CN101558135A (zh) 2006-08-16 2007-08-15 含氧化合物的流化催化裂化
JP2009524192A JP2010500464A (ja) 2006-08-16 2007-08-15 含酸素化合物の流動接触分解法
KR1020097005405A KR20090052363A (ko) 2006-08-16 2007-08-15 산소화 화합물의 유동상 촉매 분해 방법
MX2009001721A MX2009001721A (es) 2006-08-16 2007-08-15 Craqueo catalitico fluido de compuestos oxigenados.
CO09027098A CO6190561A2 (es) 2006-08-16 2009-03-16 Craqueo catalitico fluido de compuestos oxigenados
US13/196,489 US8524960B2 (en) 2006-08-16 2011-08-02 Fluid catalytic cracking of oxygenated compounds

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP06118982A EP1892280A1 (en) 2006-08-16 2006-08-16 Fluid catalytic cracking of oxygenated compounds

Publications (1)

Publication Number Publication Date
EP1892280A1 true EP1892280A1 (en) 2008-02-27

Family

ID=37685085

Family Applications (2)

Application Number Title Priority Date Filing Date
EP06118982A Withdrawn EP1892280A1 (en) 2006-08-16 2006-08-16 Fluid catalytic cracking of oxygenated compounds
EP07802626A Withdrawn EP2059576A2 (en) 2006-08-16 2007-08-15 Fluid catalytic cracking of oxygenated compounds

Family Applications After (1)

Application Number Title Priority Date Filing Date
EP07802626A Withdrawn EP2059576A2 (en) 2006-08-16 2007-08-15 Fluid catalytic cracking of oxygenated compounds

Country Status (10)

Country Link
US (2) US8207385B2 (pt)
EP (2) EP1892280A1 (pt)
JP (1) JP2010500464A (pt)
KR (1) KR20090052363A (pt)
CN (1) CN101558135A (pt)
BR (1) BRPI0715873A2 (pt)
CA (1) CA2660755C (pt)
CO (1) CO6190561A2 (pt)
MX (1) MX2009001721A (pt)
WO (1) WO2008020047A2 (pt)

Cited By (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090318742A1 (en) * 2006-07-13 2009-12-24 China Petroleum & Chemical Corporation Process for combining the catalytic conversion of organic oxygenates and the catalytic conversion of hydrocarbons
WO2010002886A1 (en) * 2008-06-30 2010-01-07 Kior, Inc. Producing fuel and speciality chemicals from biomass containing triglycerides and cellulose
WO2009111026A3 (en) * 2008-03-04 2010-01-28 University Of Massachusetts Catalytic pyrolysis of solid biomass and related biofuels, aromatic, and olefin compounds
WO2010002792A3 (en) * 2008-06-30 2010-05-06 Kior, Inc. Co-processing solid biomass in a conventional petroleum refining process unit
WO2011103313A3 (en) * 2010-02-17 2011-12-29 Virginia Tech Intellectual Properties, Inc. Production of pyrolysis oil
WO2012083999A1 (en) * 2010-12-20 2012-06-28 Shell Internationale Research Maatschappij B.V. Process for catalytic cracking of a lipid - containing feedstock derived from microalgae to produce hydrocarbons
WO2012083998A1 (en) * 2010-12-20 2012-06-28 Shell Internationale Research Maatschappij B.V. Process for catalytic cracking of a lipid-containing feedstock derived from microalgae to produce hydrocarbons
WO2012091815A1 (en) 2010-12-27 2012-07-05 Conocophillips Company Integrated fcc biomass pyrolysis/upgrading
WO2012136955A1 (en) * 2011-04-08 2012-10-11 Aston University Methods and apparatus for the production of fuel
US8288600B2 (en) 2009-05-22 2012-10-16 Kior Inc. Methods for co-processing of biomass and petroleum feed
WO2012143564A1 (en) * 2011-04-21 2012-10-26 Shell Internationale Research Maatschappij B.V. Process for converting a solid biomass material
WO2012143573A1 (en) * 2011-04-21 2012-10-26 Shell Internationale Research Maatschappij B.V. Process for converting a solid biomass material
WO2012143567A1 (en) * 2011-04-21 2012-10-26 Shell Internationale Research Maatschappij B.V. Process for converting a solid biomass material
WO2012143551A1 (en) * 2011-04-21 2012-10-26 Shell Internationale Research Maatschappij B.V. Process for converting a solid biomass material
WO2012143549A1 (en) * 2011-04-21 2012-10-26 Shell Internationale Research Maatschappij B.V. Improvements to separation of product streams
WO2012143550A1 (en) * 2011-04-21 2012-10-26 Shell Internationale Research Maatschappij B.V. Process for converting a solid biomass material
WO2013102070A3 (en) * 2011-12-30 2013-08-29 Shell Oil Company Process for converting a solid biomass material
WO2014092896A1 (en) * 2012-12-10 2014-06-19 Exxonmobil Research And Engineering Company Catalytic cracking process for biofeeds
EP2595941A4 (en) * 2010-07-23 2014-07-30 Kior Inc MULTI-STAGE CONVERSION OF A BIOMASS
US9169444B2 (en) 2011-04-21 2015-10-27 Shell Oil Company Liquid fuel composition
US9169442B2 (en) 2009-09-09 2015-10-27 University Of Massachusetts Systems and processes for catalytic pyrolysis of biomass and hydrocarbonaceous materials for production of aromatics with optional olefin recycle, and catalysts having selected particle size for catalytic pyrolysis
EP2297279A4 (en) * 2008-05-29 2015-12-23 Kellogg Brown & Root Llc FCC FOR LIGHTWEIGHT HYDROCARBON INGREDIENTS WITH BALANCED HEAT BALANCE
WO2019097199A1 (en) * 2017-11-15 2019-05-23 Petróleo Brasileiro S.A. - Petrobras Process for obtaining a renewable hydrocarbon stream suitable as a component of gasoline formulations, renewable hydrocarbon stream, and gasoline formulation
WO2019165350A1 (en) * 2018-02-26 2019-08-29 Bischof Steven M Normal alpha olefin synthesis using dehydroformylation or dehydroxymethylation
US10435334B2 (en) 2016-11-10 2019-10-08 Chevron Phillips Chemical Company Lp Normal alpha olefin synthesis using metathesis and dehydroformylation
US11123723B2 (en) 2018-02-26 2021-09-21 The Regents Of The University Of California Oxidative dehydroxymethylation of alcohols to produce olefins
US12151993B2 (en) 2021-09-10 2024-11-26 Chevron Phillips Chemical Company Lp Selective 1-hexene/1-octene production with 1-decene

Families Citing this family (67)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007112570A1 (en) 2006-04-03 2007-10-11 Pharmatherm Chemicals Inc. Thermal extraction method and product
JP5013396B2 (ja) * 2006-09-01 2012-08-29 独立行政法人産業技術総合研究所 炭素数３の多価アルコールの脱水／水素化用触媒及びそれを用いた炭化水素の製造方法
EP2053114A1 (en) * 2007-10-18 2009-04-29 BIOeCON International Holding N.V. Process for reducing the oxygen content of high-oxygen feedstocks
US7905990B2 (en) 2007-11-20 2011-03-15 Ensyn Renewables, Inc. Rapid thermal conversion of biomass
US8673262B2 (en) * 2008-04-23 2014-03-18 Her Majesty The Queen In Right Of Canada, As Represented By The Minister Of Natural Resources Production of hydrogen from oxygenated hydrocarbons
BRPI0804120A2 (pt) * 2008-09-09 2010-07-06 Petróleo Brasileiro S/A - Petrobras método para produção de eteno e gás de sìntese em leito fluidizado circulante
DE102008042498A1 (de) * 2008-09-30 2010-04-01 Evonik Degussa Gmbh Verfahren zur Pyrolyse von Kohlehydraten
US8900416B2 (en) 2009-02-24 2014-12-02 University Of Georgia Research Foundation, Inc. Production of higher quality bio-oils by in-line esterification of pyrolysis vapor
DK2430124T3 (en) * 2009-05-05 2019-03-11 Kior Inc IMPROVED CATALYST / BIOMASS MIXTURE IN TRANSPORT REACTOR
CN102040438A (zh) * 2009-10-13 2011-05-04 中国石油化工股份有限公司 同轴式内嵌提升管循环反应-再生装置
US20130184505A1 (en) * 2009-10-27 2013-07-18 Ignite Energy Resources Limited Methods for Producing Hydrocarbon Products from Bio-Oils and/or Coal-Oils
US8519203B2 (en) * 2010-02-17 2013-08-27 Uop Llc Low oxygen biomass-derived pyrolysis oils and methods for producing the same
US8604260B2 (en) 2010-05-18 2013-12-10 Kior, Inc. Biomass pyrolysis conversion process with high olefin production and upgrade
US20110284359A1 (en) 2010-05-20 2011-11-24 Uop Llc Processes for controlling afterburn in a reheater and for controlling loss of entrained solid particles in combustion product flue gas
US8499702B2 (en) 2010-07-15 2013-08-06 Ensyn Renewables, Inc. Char-handling processes in a pyrolysis system
US8057641B2 (en) * 2010-07-19 2011-11-15 Kior Inc. Method and apparatus for pyrolysis of a biomass
CN103201357A (zh) * 2010-11-12 2013-07-10 国际壳牌研究有限公司 制备生物燃料和/或生物化学品的方法
CN102463081A (zh) * 2010-11-17 2012-05-23 中国石油化工股份有限公司 制备低碳烯烃的反应装置
WO2012092468A1 (en) * 2010-12-30 2012-07-05 Kior Inc. Production of renewable biofuels
US9441887B2 (en) 2011-02-22 2016-09-13 Ensyn Renewables, Inc. Heat removal and recovery in biomass pyrolysis
EP2699646A1 (en) * 2011-04-21 2014-02-26 Shell Internationale Research Maatschappij B.V. Process for regenerating a coked catalytic cracking catalyst
CN102220167B (zh) * 2011-05-11 2013-12-25 华北电力大学 一种生物质油改质和c4烃催化裂解的组合工艺及装置
WO2013032672A1 (en) * 2011-09-01 2013-03-07 University Of Massachusetts Method for producing fluid hydrocarbons
US9347005B2 (en) 2011-09-13 2016-05-24 Ensyn Renewables, Inc. Methods and apparatuses for rapid thermal processing of carbonaceous material
US10041667B2 (en) 2011-09-22 2018-08-07 Ensyn Renewables, Inc. Apparatuses for controlling heat for rapid thermal processing of carbonaceous material and methods for the same
US9044727B2 (en) 2011-09-22 2015-06-02 Ensyn Renewables, Inc. Apparatuses and methods for controlling heat for rapid thermal processing of carbonaceous material
US10400175B2 (en) 2011-09-22 2019-09-03 Ensyn Renewables, Inc. Apparatuses and methods for controlling heat for rapid thermal processing of carbonaceous material
SG188753A1 (en) * 2011-09-30 2013-04-30 Bharat Petroleum Corp Ltd Sulphur reduction catalyst additive composition in fluid catalytic cracking and method of preparation thereof
CN106085469B (zh) * 2011-11-04 2020-01-17 国际热化学恢复股份有限公司 用于原料向油和气的弹性转化的系统和方法
US9109177B2 (en) * 2011-12-12 2015-08-18 Ensyn Renewables, Inc. Systems and methods for renewable fuel
GB2497543B (en) * 2011-12-13 2015-09-02 Future Blends Ltd Catalytic cracking of pyrolysis derived organic molecules
US20130178672A1 (en) * 2012-01-06 2013-07-11 Shell Oil Company Process for making a distillate product and/or c2-c4 olefins
US20150337207A1 (en) * 2012-01-06 2015-11-26 Shell Oil Company Process for making a distillate product and/or c2-c4 olefins
EP2841536A1 (en) 2012-04-23 2015-03-04 Shell Internationale Research Maatschappij B.V. Process for converting a solid biomass material
US9222032B2 (en) 2012-05-01 2015-12-29 Mississippi State University Composition and methods for improved fuel production
US20140004610A1 (en) * 2012-06-28 2014-01-02 Uop Llc Processes and apparatuses for converting a feedstock
US9670413B2 (en) 2012-06-28 2017-06-06 Ensyn Renewables, Inc. Methods and apparatuses for thermally converting biomass
US9556391B2 (en) 2012-07-13 2017-01-31 Phillips 66 Company Method for producing renewable hydrogen from biomass derivatives using steam reforming technology
US9523042B2 (en) 2012-07-31 2016-12-20 Uop Llc Methods and fuel processing apparatuses for upgrading a pyrolysis oil stream and a hydrocarbon stream
US10166519B2 (en) 2012-07-31 2019-01-01 Uop Llc Methods and fuel processing apparatuses for upgrading a pyrolysis oil stream and a hydrocarbon stream
US9663729B2 (en) 2012-07-31 2017-05-30 Uop Llc Methods and fuel processing apparatuses for upgrading a pyrolysis oil stream and a hydrocarbon stream
BR112015009011A8 (pt) * 2012-10-31 2019-07-16 Shell Int Research método para produzir e processar um produto de reação de glicol obtido junto com digestão hidrotérmica de sólidos de biomassa celulósica
CN104884580A (zh) * 2012-10-31 2015-09-02 国际壳牌研究有限公司 用于将由纤维素生物质固体的水热消解获得的二醇反应产物转化为经干燥的一元醇进料的方法
US20140296594A1 (en) * 2013-03-28 2014-10-02 Shell Oil Company Process for the fluid catalytic cracking of oxygenated hydrocarbon compounds from biological origin
CN104073292B (zh) * 2013-03-28 2019-07-23 中国石油大学(华东) 使来自生物来源的氧化烃化合物流化催化裂化的方法
CN104073280B (zh) * 2013-03-28 2019-07-26 中国石油大学(华东) 流化催化裂化生物来源含氧烃化合物的方法
CN103215068B (zh) * 2013-05-07 2015-06-03 武汉凯迪工程技术研究总院有限公司 一种生物质热解油的改性方法
AR097135A1 (es) 2013-06-26 2016-02-24 Ensyn Renewables Inc Sistemas y métodos para combustible renovable
KR101790987B1 (ko) * 2014-05-21 2017-10-27 한양대학교 산학협력단 글리세롤을 이용한 바이오 방향족 화합물의 제조방법
WO2016053780A1 (en) 2014-09-29 2016-04-07 Uop Llc Methods for reducing flue gas emissions from fluid catalytic cracking unit regenerators
DK3337966T3 (da) 2015-08-21 2022-02-28 Ensyn Renewables Inc Opvarmningssystem med flydende biomasse
JP6654384B2 (ja) * 2015-09-15 2020-02-26 株式会社日本触媒 オレフィン化合物の製造方法
CN105218289B (zh) * 2015-10-15 2017-08-01 浙江大学 一种不饱和脂肪酸原位加氢脱羧制备长链烷烃的方法
FI127519B (en) 2015-12-31 2018-08-15 Neste Oyj Process for producing high octane fuel component from renewable raw material
CN110072973A (zh) * 2016-12-14 2019-07-30 埃克森美孚研究工程公司 在流化催化裂化器中转化含氧化合物的方法
CA3048681A1 (en) 2016-12-29 2018-07-05 Ensyn Renewables, Inc. Demetallization of liquid biomass
WO2018147281A1 (ja) * 2017-02-07 2018-08-16 国立大学法人信州大学 炭化水素の製造方法、その製造装置、その製造システム、及び、バイオクルードの製造方法
JP2020019912A (ja) * 2018-08-03 2020-02-06 国立大学法人信州大学 炭化水素の製造方法およびバイオクルードの製造方法
US10479943B1 (en) * 2018-08-17 2019-11-19 Chevron U.S.A. Inc. Fluid catalytic cracking process employing a lipid-containing feedstock
CA3112833A1 (en) * 2018-09-25 2020-04-02 Exxonmobil Research And Engineering Company Co-processing hydrothermal liquefaction oil and co-feed to produce biofuels
CA3147048A1 (en) * 2019-07-11 2021-01-14 Spraying Systems Co. Catalytic cracking system with bio-oil processing
WO2021081089A1 (en) * 2019-10-23 2021-04-29 Phillips 66 Company Dual stage light alkane conversion to fuels
US10947458B1 (en) 2020-03-18 2021-03-16 Chevron U.S.A. Inc. Upgrading of renewable feedstocks with spent equilibrium catalyst
FI129351B (en) * 2020-11-06 2021-12-31 Neste Oyj Process for the production of bio - based hydrocarbons
US11680210B2 (en) * 2021-11-04 2023-06-20 Chevron U.S.A. Inc. Catalytic cracking of glyceride oils with deactivated phosphorus-containing ZSM-5 light olefins additives
CN115521186A (zh) * 2022-10-06 2022-12-27 新疆大学 一种生物质经两步转化过程制备低碳烯烃的方法
EP4667551A1 (en) * 2024-06-18 2025-12-24 Neste Oyj A method for producing propylene

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS562389A (en) * 1979-06-21 1981-01-12 Nippon Kaihatsu Kogyo Kk Catalytic cracking of heavy oil
CA1123774A (en) * 1980-02-25 1982-05-18 Marten Ternan Catalytic conversion of heavy hydrocarbon materials
US20030127358A1 (en) * 2002-01-10 2003-07-10 Letzsch Warren S. Deep catalytic cracking process

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4503278A (en) * 1982-09-30 1985-03-05 Mobil Oil Corporation Process for converting carbohydrates to hydrocarbons
BR8304794A (pt) * 1983-09-02 1985-04-09 Petroleo Brasileiro Sa Processo para a producao de gasolina de lata octanagem
US4880473A (en) * 1988-04-01 1989-11-14 Canadian Patents & Development Ltd. Process for the production of fermentable sugars from biomass
US5196633A (en) * 1990-01-25 1993-03-23 Mobil Oil Corp. Catalytic conversion
US5298155A (en) * 1990-02-27 1994-03-29 Exxon Research & Engineering Co. Controlling yields and selectivity in a fluid catalytic cracker unit
JPH0562389A (ja) 1991-09-06 1993-03-12 Nec Software Ltd コンピユータ用フレキシブルデイスク制御装置
US6187982B1 (en) * 1999-10-15 2001-02-13 Mobil Oil Corporation Process for converting dienes and oxygenates to para-xylene and light olefins
EP1517747A1 (en) * 2002-06-28 2005-03-30 Albemarle Netherlands B.V. Fcc catalyst for reducing the sulfur content in gasoline and diesel
BRPI0502577B1 (pt) * 2005-07-07 2015-11-03 Petroleo Brasileiro Sa processo de craqueamento catalítico para produção de diesel a partir de óleos vegetais
US20090026112A1 (en) * 2006-02-09 2009-01-29 Jan Lodewijk Maria Dierickx Fluid catalytic cracking process

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS562389A (en) * 1979-06-21 1981-01-12 Nippon Kaihatsu Kogyo Kk Catalytic cracking of heavy oil
CA1123774A (en) * 1980-02-25 1982-05-18 Marten Ternan Catalytic conversion of heavy hydrocarbon materials
US20030127358A1 (en) * 2002-01-10 2003-07-10 Letzsch Warren S. Deep catalytic cracking process

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
CRAIG HULET ET AL: "A Review of Short Residence Time Cracking Processes", INTERNATIONAL JOURNAL OF CHEMICAL REACTOR ENGINEERING, BERKELEY ELECTRONIC PRESS, BERKELEY, CA, US, vol. 3, 2005, pages 1 - 76, XP008080585, ISSN: 1542-6580 *
LIN ET AL: "Catalytic conversion of commingled polymer waste into chemicals and fuels over spent FCC commercial catalyst in a fluidised-bed reactor", APPLIED CATALYSIS B: ENVIRONMENTAL, ELSEVIER, vol. 69, no. 3-4, 14 August 2006 (2006-08-14), pages 145 - 153, XP005812415, ISSN: 0926-3373 *

Cited By (39)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8373013B2 (en) * 2006-07-13 2013-02-12 China Petroleum & Chemical Corporation Process for combining the catalytic conversion of organic oxygenates and the catalytic conversion of hydrocarbons
US20090318742A1 (en) * 2006-07-13 2009-12-24 China Petroleum & Chemical Corporation Process for combining the catalytic conversion of organic oxygenates and the catalytic conversion of hydrocarbons
WO2009111026A3 (en) * 2008-03-04 2010-01-28 University Of Massachusetts Catalytic pyrolysis of solid biomass and related biofuels, aromatic, and olefin compounds
US8864984B2 (en) 2008-03-04 2014-10-21 University Of Massachusetts Catalytic pyrolysis of solid biomass and related biofuels, aromatic, and olefin compounds
US8277643B2 (en) 2008-03-04 2012-10-02 University Of Massachusetts Catalytic pyrolysis of solid biomass and related biofuels, aromatic, and olefin compounds
EP2297279A4 (en) * 2008-05-29 2015-12-23 Kellogg Brown & Root Llc FCC FOR LIGHTWEIGHT HYDROCARBON INGREDIENTS WITH BALANCED HEAT BALANCE
WO2010002886A1 (en) * 2008-06-30 2010-01-07 Kior, Inc. Producing fuel and speciality chemicals from biomass containing triglycerides and cellulose
WO2010002792A3 (en) * 2008-06-30 2010-05-06 Kior, Inc. Co-processing solid biomass in a conventional petroleum refining process unit
US9944837B2 (en) 2008-06-30 2018-04-17 Inaeris Technologies, Llc Co-processing solid biomass in a conventional petroleum refining process unit
US8288600B2 (en) 2009-05-22 2012-10-16 Kior Inc. Methods for co-processing of biomass and petroleum feed
US9453166B2 (en) 2009-09-09 2016-09-27 University Of Massachusetts Systems and processes for catalytic pyrolysis of biomass and hydrocarbonaceous materials for production of aromatics with optional olefin recycle, and catalysts having selected particle size for catalytic pyrolysis
US9169442B2 (en) 2009-09-09 2015-10-27 University Of Massachusetts Systems and processes for catalytic pyrolysis of biomass and hydrocarbonaceous materials for production of aromatics with optional olefin recycle, and catalysts having selected particle size for catalytic pyrolysis
WO2011103313A3 (en) * 2010-02-17 2011-12-29 Virginia Tech Intellectual Properties, Inc. Production of pyrolysis oil
EP2595941A4 (en) * 2010-07-23 2014-07-30 Kior Inc MULTI-STAGE CONVERSION OF A BIOMASS
US9394487B2 (en) 2010-07-23 2016-07-19 Inaeris Technologies, Llc Multi-stage biomass conversion
WO2012083998A1 (en) * 2010-12-20 2012-06-28 Shell Internationale Research Maatschappij B.V. Process for catalytic cracking of a lipid-containing feedstock derived from microalgae to produce hydrocarbons
WO2012083999A1 (en) * 2010-12-20 2012-06-28 Shell Internationale Research Maatschappij B.V. Process for catalytic cracking of a lipid - containing feedstock derived from microalgae to produce hydrocarbons
WO2012091815A1 (en) 2010-12-27 2012-07-05 Conocophillips Company Integrated fcc biomass pyrolysis/upgrading
US8829258B2 (en) 2010-12-27 2014-09-09 Phillips 66 Company Integrated FCC biomass pyrolysis/upgrading
WO2012136955A1 (en) * 2011-04-08 2012-10-11 Aston University Methods and apparatus for the production of fuel
US9238779B2 (en) 2011-04-21 2016-01-19 Shell Oil Company Process for converting a solid biomass material
WO2012143567A1 (en) * 2011-04-21 2012-10-26 Shell Internationale Research Maatschappij B.V. Process for converting a solid biomass material
WO2012143564A1 (en) * 2011-04-21 2012-10-26 Shell Internationale Research Maatschappij B.V. Process for converting a solid biomass material
US9249362B2 (en) 2011-04-21 2016-02-02 Shell Oil Company Separation of product streams
US9169444B2 (en) 2011-04-21 2015-10-27 Shell Oil Company Liquid fuel composition
WO2012143549A1 (en) * 2011-04-21 2012-10-26 Shell Internationale Research Maatschappij B.V. Improvements to separation of product streams
US9217111B2 (en) 2011-04-21 2015-12-22 Shell Oil Company Process for converting a solid biomass material
WO2012143551A1 (en) * 2011-04-21 2012-10-26 Shell Internationale Research Maatschappij B.V. Process for converting a solid biomass material
WO2012143573A1 (en) * 2011-04-21 2012-10-26 Shell Internationale Research Maatschappij B.V. Process for converting a solid biomass material
US8779225B2 (en) 2011-04-21 2014-07-15 Shell Oil Company Conversion of a solid biomass material
WO2012143550A1 (en) * 2011-04-21 2012-10-26 Shell Internationale Research Maatschappij B.V. Process for converting a solid biomass material
WO2013102070A3 (en) * 2011-12-30 2013-08-29 Shell Oil Company Process for converting a solid biomass material
WO2014092896A1 (en) * 2012-12-10 2014-06-19 Exxonmobil Research And Engineering Company Catalytic cracking process for biofeeds
US10435334B2 (en) 2016-11-10 2019-10-08 Chevron Phillips Chemical Company Lp Normal alpha olefin synthesis using metathesis and dehydroformylation
WO2019097199A1 (en) * 2017-11-15 2019-05-23 Petróleo Brasileiro S.A. - Petrobras Process for obtaining a renewable hydrocarbon stream suitable as a component of gasoline formulations, renewable hydrocarbon stream, and gasoline formulation
WO2019165350A1 (en) * 2018-02-26 2019-08-29 Bischof Steven M Normal alpha olefin synthesis using dehydroformylation or dehydroxymethylation
US10723672B2 (en) 2018-02-26 2020-07-28 Chervon Phillips Chemical Company Lp Normal alpha olefin synthesis using dehydroformylation or dehydroxymethylation
US11123723B2 (en) 2018-02-26 2021-09-21 The Regents Of The University Of California Oxidative dehydroxymethylation of alcohols to produce olefins
US12151993B2 (en) 2021-09-10 2024-11-26 Chevron Phillips Chemical Company Lp Selective 1-hexene/1-octene production with 1-decene

Also Published As

Publication number Publication date
CN101558135A (zh) 2009-10-14
WO2008020047A3 (en) 2008-04-03
KR20090052363A (ko) 2009-05-25
EP2059576A2 (en) 2009-05-20
BRPI0715873A2 (pt) 2013-08-13
CO6190561A2 (es) 2010-08-19
CA2660755A1 (en) 2008-02-21
US20100222620A1 (en) 2010-09-02
WO2008020047A2 (en) 2008-02-21
JP2010500464A (ja) 2010-01-07
US8207385B2 (en) 2012-06-26
US20120198756A1 (en) 2012-08-09
US8524960B2 (en) 2013-09-03
MX2009001721A (es) 2009-05-13
CA2660755C (en) 2014-12-16

Similar Documents

Publication Publication Date Title
US8207385B2 (en) Fluid catalytic cracking of oxygenated compounds
Corma et al. Processing biomass-derived oxygenates in the oil refinery: Catalytic cracking (FCC) reaction pathways and role of catalyst
Adjaye et al. Production of hydrocarbons by catalytic upgrading of a fast pyrolysis bio-oil. Part II: Comparative catalyst performance and reaction pathways
Ding et al. Improving hydrocarbon yield from catalytic fast co-pyrolysis of hemicellulose and plastic in the dual-catalyst bed of CaO and HZSM-5
Valle et al. Recent research progress on bio‐oil conversion into bio‐fuels and raw chemicals: a review
Zhao et al. Upgrading pyrolysis oil over Ni/HZSM‐5 by cascade reactions
Fogassy et al. Biomass derived feedstock co-processing with vacuum gas oil for second-generation fuel production in FCC units
Al-Sabawi et al. Fluid catalytic cracking of biomass-derived oils and their blends with petroleum feedstocks: a review
Gayubo et al. Attenuation of catalyst deactivation by cofeeding methanol for enhancing the valorisation of crude bio-oil
US8501043B2 (en) Processing of biomass-derived oxygenates with particles comprising a coke deposit
Wan et al. Direct catalytic upgrading of biomass pyrolysis vapors by a dual function Ru/TiO2 catalyst
US8513476B2 (en) Process for producing light olefins from a feed containing triglycerides
Bertero et al. Conversion of pine sawdust bio-oil (raw and thermally processed) over equilibrium FCC catalysts
JP2013545841A (ja) バイオ燃料及び／又は生化学物質の製造方法
CN108017487B (zh) 含有含氧化合物原料制芳烃两段反应的方法
Cai et al. Upgrading of bio-oil aqueous fraction by dual-stage hydrotreating–cocracking with methanol
WO2015116385A1 (en) Method of biomass conversion using a multi-functional catalyst system
WO2018089520A1 (en) Fluidized upgrading/hydrostabilizing of pyrolysis vapors
Shimada et al. Hydrocarbon fuel production from lignocellulosic biomass by solvolysis and catalytic cracking
Iliopoulou et al. Nanocatalysis in the fast pyrolysis of lignocellulosic biomass
Alvarez et al. Bio-oil production
Triantafyllidis et al. 5. State-of-the-art in biomass fast pyrolysis using acidic catalysts: direct comparison between microporous zeolites, mesoporous aluminosilicates and hierarchical zeolites
Gong et al. Biobased paraxylene
Seshan Catalytic pyrolysis of lignocellulosic biomass
Guo et al. Catalytic cracking characteristics of bio-oil molecular distillation fraction

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL BA HR MK YU

AKX Designation fees paid
REG Reference to a national code

Ref country code: DE

Ref legal event code: 8566

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20080828